https://doi.org/10.
1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3), 191–204
Continuous Production of Squalane Using 3D
Printed Catalytic Supports
Additive manufacturing confers advantages for catalyst support design
Sonia García*, Stephen Poulston,
Deena Modeshia
Johnson Matthey, Blounts Court, Sonning
Common, Reading, RG4 9HN, UK
Petr Stavarek, Massimo Ujcic,
Farzad Lali
Institute of Chemical Process Fundamentals of
the CAS, v. v. i., Rozvojova 2/135, CZ-165 02
Prague 6 - Suchdol, Czech Republic
Manuel A. Alves, José D. Araújo
The Faculty of Engineering of the University of
Porto, Department of Chemical Engineering,
Rua Dr Roberto Frias, 4200-465, Porto, Portugal
Michael Krusche, Frank Ullrich,
Diana Maier
Advanced Machinery & Technology Chemnitz
GmbH (AMTECH), Annaberger Strasse 240,
09125 Chemnitz, Germany
*E-mail: sonia.garcia@matthey.com
Squalene (SQE) was fully converted into squalane
(SQA) in a continuous reactor. The design of a
three-dimensional (3D) printed support allowed
selectivity to be tuned towards squalane. The
advantages of being able to design the geometry of
the catalytic support using 3D printing technology
are presented in this paper.
+ 6H2
Squalene
Scheme I
191 © 2019 Johnson Matthey
www.technology.matthey.com
Introduction
SQA is a colourless, odourless and tasteless
hydrocarbon oil notably resistant to oxidation. It
is known to act as an immune system stimulant
as well as antioxidant agent. These properties are
contributing to it increasingly being used in the
pharmaceutical industry. For instance, emulsions
of SQA with surfactants are added to vaccines to
enhance the immune response (1). A number of
studies have proved the properties of SQE and SQA
as an antioxidant, drug carrier and emollient (2). The
pharmaceutical industry uses SQA in vaccines and in
anticancer treatment. SQA and SQE have been proven
to have very little toxicity and improve the antibody
responses to antigens in a number of primates (3).
Due to its capability to penetrate the human
skin, SQA is best known for its applications in the
cosmetic industry. The main interest is to transport
and increase absorption of other active components
(4). The main uses of SQA are shown in Figure 1.
The use of SQA is preferred for all of these uses to
SQE as this molecule is stable and not susceptible
to oxidation (5).
SQA is produced from hydrogenation of SQE,
which is a non-saponifiable component of natural
lipids. The reaction is shown in Scheme I.
SQE used to be obtained from shark liver oil,
although this practice is generally not accepted by
cosmetic manufacturers. Today most of the SQE
is derived from vegetable sources, such as olive
Squalane
https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

developed catalyst on a ceramic 3D printed support

Pharmaceutical Food to improve the process from the points of view of
industry supplements
8% both catalyst activity and heat transfer.
23%
The intensification of a catalytic reactor is mainly
dependent on the operational limitations of the
system and requirements related to the specific
chemical reactions. For that purpose, working on
the geometry of the catalytic support is one way to
reach the desired improvements, which implies the
definition of an adequate approach to design such
Cosmetics
3D structures.
69%
In a continuous flow reactor, the catalyst needs
Fig. 1. Uses of SQA in 2014 to be shaped in a form that suits both the process
and chemical reaction itself. The shape must
consider factors such as mass transfer limitations
Table I SQE Purity and Cost and reduction of selectivity due to side reactions
Depending on Source (9). Packed beds of shaped supports tend to be
SQE Content, Cost, Impurities after used in continuous reactors. However, a common
source % € kg–1 hydrogenation problem due to the nature of the shape packing
Shark is their associated pressure drop (10) as well
98–99 17–19 Not significant as possible flow maldistribution. The latter can
liver oil
Sterol esters result in reactants not accessing the surface of
Olive oil 5–17 21–24
Parafins the catalyst uniformly decreasing the overall
Sugar Isosqualane performance of the process, for instance, by
92–93 22–27
cane Monocyclosqualane causing wide distribution in residence time that
lowers selectivity (9).
oil and sugarcane. The cost of SQE as well as the Digital methods allow objects to be designed
impurities present in the reactant depend on the and produced for specific applications. Optimised
source, as shown in Table I. structures offer the possibility of efficiently
The purity of SQE will affect the selectivity towards controlling the fluid dynamics and temperature
SQA. For instance, a range of different purities of uniformity (9). The work presented in this paper
SQE were studied by Pandarus et al. (4). Results uses modelling of the flow phenomena involved in
showed that under the same reaction conditions, the hydrogenation of SQE to produce a 3D structure
high purity SQE (98 wt%) achieved 99% selectivity that optimises the process.
towards SQA, whilst in a lower purity sample
(82 wt%) the selectivity was 39%.
Catalysts Used in this Study
This hydrogenation is traditionally carried out in a
batch reactor with the use of a nickel based catalyst The catalyst support was based on a ceramic
(6) or more recently palladium catalysts (7). The precursor that is commercially available in the form
disadvantages of the traditional process are the of cylindrical pellets and served as a benchmarking
fast and irreversible Ni catalyst deactivation and Ni material for the developed 3D printed catalysts.
leaching that requires product purification. The cost The catalysts were prepared by 3D printing
of the hydrogenation of SQE comprises ca. 40% of to provide a precursor that was consequently
the total price of the entire process (8). Therefore, thermally converted to the ceramic of a desired
a new catalyst that would overcome disadvantages structure. The structure was then impregnated with
of the traditional process might bring considerable Pd. A novel preparation method was developed in
cost savings. Nevertheless, the other challenge Johnson Matthey, UK, to ensure high dispersion
of this reaction is its extreme exothermicity and high stability for Pd on ceramic. A summary
(ΔHr = –604.26 kJ mol–1). It is therefore important of the physical characteristics of the samples is
to consider that the intensified catalytic system will shown in Table II.
generate more reaction heat, which needs to be All the catalysts were supplied by Johnson Matthey
removed from the process. and consisted of 2 wt% Pd developmental samples.
This paper presents results on hydrogenation The testing was carried out using 3.5 mmolPd per
of SQE in a continuous reactor with use of newly 100 g of SQE.

192 © 2019 Johnson Matthey

https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)
Table II  Catalysts Used for Hydrogenation of SQE
Catalyst 3 mm pellets 1 mm pellets
Form Extrudates (cylinders) Extrudates (cylinders)
Particle
3 x 3 mm 1 x 3 mm
size
Shape
Different particle sizes of conventional extrudates
were used in an attempt to study the effect of
diffusion limitation. Subsequently, the conventional
and 3D printed ceramics were compared using
crushed 3D printed supports sieved to the same
size as the conventional pellets. In the case of
crushed 3D printed catalyst, the crushing process
preceded the catalyst impregnation to avoid its
distribution inhomogeneity.
Design of 3D Printed Supports for a
Continuous Reactor
Tailored supports were designed for the
hydrogenation of SQE in a continuous reactor.
Because of the extreme exothermicity of this
relatively fast reaction, it is desired to control
the reaction rate in a way to avoid formation of
a narrow reaction zone or hot spots especially
at the first part of a reactor. One of the possible
ways to achieve this would be to vary the metal
loading on the support. However, increasing the
loading could encourage the agglomeration of
Pd particles and lead to rapid deactivation of the
catalyst. An alternative way was to use 3D printing
technology for the design of catalytic foams with
different density. This, in turn, resulted in a way of
keeping metal loading per gram of catalyst while
varying the amount of metal in a certain part of
the reactor.
Firstly, the structure topology of the support was
chosen. Open-cell foams were selected because
this type of structure can incorporate attractive
benefits, such as suitable thermal conductivity,
depending on the chosen material, appropriate
mixing, low pressure drop and large surface area
per unit volume to increase catalytic activity.
Besides these benefits, open-cell foams also
193 © 2019 Johnson Matthey
3D printed 3D printed
(crushed)
3D structure crushed 3D structure
Irregular particles
1 x 3 mm
1–3 mm
offer the advantage of being the repetition of a
representative unit cell, which can significantly
simplify its manufacture and the modelling of the
physical phenomena involved. There is a set of
information required to fully define the geometry
of a system containing an open-cell foam support:
(a) topology of the representative unit cell;
(b) values of relevant geometric parameters of the
cell; (c) total number of unit cells present in each
direction (x, y and z), i.e. dimensions of the system
(overall or sections).
In the specific case of this work, twisted cubic
cells were chosen as the base topology due to their
simplicity. The geometric parameters to consider
were the unit cell width, struts’ diameter, twist
angle per unit length of foam and tilt angles of the
cells relative to the main flow direction.
A set of foam geometries were tested based on
different values of the referred parameters. For
each foam, a sequence of steps was followed to
assess the best options:
(a) Digital representation of the foam structure in
a stereolithography (STL) file (see Figure 2).
This file format can be used for both 3D printing
and to perform computational fluid dynamics
(CFD) modelling. The STL files were produced
by a geometry generator software based on the
input of the previously mentioned information.
The geometry generator used was Blender®
(Blender Foundation, The Netherlands), a free
software package that can work in automatic
mode using  script files programmed in the
Python language
(b) Creating a proper computational mesh for the
fluid volume. This volume is complementary to
that defined by the STL file (solid volume). The
mesh generator software was cfMesh, a tool of
OpenFOAM® (The OpenFOAM Foundation, UK)
https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

(a) (b)
(a) (b)

Inlet
(bottom view)

C/C0 ΔP × 103, bar

0 0.25 0.5 0.75 1.0 0 0.2 0.4 0.6 0.8

Fig. 3. Illustrative results of: (a) concentration;

Fig. 2. (a) Representation of one of the and (b) pressure fields in the system presented
open-cell foams tested; (b) the corresponding in Figure 2 – central longitudinal view. The results
computational mesh were obtained for a simulation replicating a tracer
test (tracer inlet concentration in the left side of
(a)) with an average inlet velocity of 0.03 m s–1
(c) Performing a CFD simulation in the mesh using a mesh corresponding to about 5% of the
previously created (step (b) above) to total reactor length
characterise the foam structure in terms of
mixing and pressure drop (see illustrative
results in Figure 3). The open source
Design 1
OpenFOAM® CFD package, which uses the
C++ programming language, was the software
used. The implemented numerical model
was prepared to include single-phase flow
and transient mass balance equations (with
diffusion, convection and the possibility of
homogeneous and heterogeneous reaction
terms) for different species
(d) The data produced by the CFD simulation
are post-processed to calculate the value of
Design 2
a previously defined objective function. This
objective function includes terms addressing
mass dispersion, pressure drop per unit length
and superficial area per unit volume.
From the set of geometries investigated, the
STL files of the two foams selected are shown
in Figure 4. Based on these files, slices of 1 cm
height were 3D printed according to both referred
designs. The corresponding values of structure
porosity (ε), specific (geometrical) surface area
(AS) and diameter of struts (dS) are shown in
Table III. For comparison, the properties of the Fig. 4. Representation of two STL files designed
for SQA production. A full view, a front view of a
beds consisting of 1 mm and 3 mm conventional
central longitudinal cut and a zoom of this cut are
pellets (extrudates) are also provided. The specific presented for each design. The zoom view contains
surface area of Design 2 foams is close to 3 mm indication of strut diameter (dS, green) and
pellets while keeping higher bed porosity, which is distance between struts (dO, red)
beneficial for lower pressure drop.
The use of two different types of structures,
as shown in Figure 5, allowed the initial part In the second part of the reactor, more metal can be
of the reactor to achieve a slower rate of SQE present per unit volume, which will allow the reaction
hydrogenation, also yielding a lower temperature to be completed to high conversion and thus high
rise that prevents possible hot spot formation. SQA yield without compromising the selectivity.

194 © 2019 Johnson Matthey

https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

Table III Parameter Values for the

Selected Open-Cell Foam
Designs and Pellets
dS ,
ε AS, m–1
mm
Design 1 0.44 (0.52a) 1080a 1.64
a a
Design 2 0.51 (0.61 ) 1420 1.0
1 mm pellets 0.38 2894 1.0
20 nm 20 nm
3 mm pellets 0.40 1266 3.0
a
Internal structure porosity without accounting for the outer
shell Fig. 6. Dark-field STEM (DF-STEM) images of
Pd/ceramic catalyst

The samples were examined in a JEM-2800

Reactor inlet
3D printed catalyst
Design 1
3D printed catalyst
Design 2
Reactor outlet
Fig. 5. Schematic of the reactor filled with the two
different types of structures, ratio of design 1 and
design 2 is 1:3
Catalyst Preparation and
Characterisation
The catalyst was prepared by impregnation of a
Pd precursor, aiming at 2 wt% Pd, on the different
ceramic supports and subsequent reduction. The
particle size of the Pd was derived from carbon
monoxide (CO) metal area measurements. The
sample was reduced under H2/N2 at 80°C for
10 min. The catalyst was then cooled under N2 to
35°C. Subsequently, pulses of CO were introduced.
A Pd:CO stoichiometry of 1:1 was assumed and the
Pd atomic area was assumed to be 0.0800 nm2. The
Pd particle size calculated from the CO adsorption
measurements was 3–8 nm (11).
Transmission Electron Microscope (JEOL, Japan)
using the following instrumental conditions:
Voltage 200 kV; C2 aperture 70 µm (Z-contrast)
imaging in scanning mode using an off-axis annular
detector. The secondary electron (SE) signal was
acquired simultaneously with the other scanning
transmission electron microscopy (STEM) images
providing topological information about the sample.
The STEM images showed the distribution of
the metal in the support. Similar distribution
was observed for different samples. Figure 6
shows the images corresponding to 1 mm pellets,
representative of the catalysts used in the study.
The bright areas indicate the location of Pd on the
surface of the ceramic material. These images
(Figure 6) illustrate a good dispersion and metal
distribution of the metallic particles. The particle
size was determined to be between 2 nm and
6 nm, similar to those observed via CO metal area.
The metal loading for the 3D printed catalysts
was kept constant at 2 wt% Pd. The same Johnson
Matthey developmental synthetic method was
followed for the samples using the 3D printed
support.
The metal concentration on the 3D printed foam
was investigated via electron probe microanalysis
(EPMA) and results for the areas illustrated in
Figure 7 are presented in Figure 8. Although the
centre of the foams presented lower Pd density,
EPMA analysis showed metal present in the
inner areas of the support, showing a gradient of
concentration.
Results and Discussion
Batch Reactor Testing
Traditionally, hydrogenation of SQE is carried out
in a batch reactor using Ni catalyst with reaction

195 © 2019 Johnson Matthey

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A
B

Original catalyst Areas investigated

Fig. 7. Areas studied by EPMA for catalytic foams for hydrogenation of SQE

(a) (b)

–92
4.8 4.8
4.6 4.6
4.4
4.2
–89 4.4
4.2
–Y (–1 mm) [1.794 mm]

4 4

–Y (–1 mm) [1.794 mm]

3.8 3.8
–92.5 3.6
3.4
3.6
3.4
3.2 3.2
3 3
–89.5

Pd wt%
Pd wt%

2.8 2.8
2.6 2.6
2.4 2.4
2.2 2.2
–93 2 2
1.8 1.8
1.6 1.6
1.4
1.2
–90 1.4
1.2
1 1
0.8 0.8
–93.5 0.6
0.4
0.6
0.4
0.2 0.2
0 0
–90.5
–74 –73.5 –73 –72.5 –66.5 –66 –65.5
–X (–1 mm) [1.794 mm] –X (–1 mm) [1.794 mm]

(c) (d)

4.8 4.8
–81.5 4.6 4.6
4.4 4.4
4.2 –81 4.2
–Y (–1 mm) [1.794 mm]

–Y (–1 mm) [1.794 mm]

4 4
3.8 3.8
3.6 3.6
3.4 3.4
–82 3.2 3.2
3
3 Pd wt%
–81.5 2.8
Pd wt%

2.8
2.6 2.6
2.4 2.4
2.2 2.2
2 2
1.8 1.8
–82.5 1.6 1.6
1.4 1.4
1.2 –82 1.2
1 1
0.8 0.8
0.6 0.6
0.4 0.4
–83 0.2 0.2
0
0

–73 –72.5 –72 –79.5 –79 –78.5

–X (–1 mm) [1.794 mm] –X (–1 mm) [1.794 mm]

Fig. 8. Metal distribution for Pd/3D ceramic printed foams: (a) A; (b) B; (c) C; (d) D (see Figure 7)

conditions changing in a series of steps. High and hydrogen pressure are gradually increased to
temperatures during the first steps are typically compensate for catalyst deactivation.
avoided since the reaction tends to yield undesired From the mechanistic point of view, hydrogenation
products such as cyclosqualanes. Therefore, to of SQE to SQA proceeds through formation of
obtain high SQA yields usually the temperature numerous amounts of partially hydrogenated

196 © 2019 Johnson Matthey

https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

100 100

90

CSQE/C0SQE, yieldSQA, %
80 80

70
Yield SQA, %

60 60
50
40 40
30
20 3 × 3 mm pellets 20 200 ºC
1 × 3 mm pellets 180 ºC
10 3D printed 160 ºC
0 0
00:00 01:00 02:00 03:00 04:00 05:00 06:00 00:00 01:00 02:00 03:00 04:00 05:00
Time, hh:mm Time, hh:mm

Fig. 9. SQE hydrogenation: comparison of different Fig. 10. SQE hydrogenation: temperature effect,
catalysts, 2% Pd/ceramic, 180°C, 20 bar, 10% SQE 2% Pd/ceramic, 3 × 3 mm pellets, 20 bar, 10%
(marine) in an organic solvent SQE (marine) in an organic solvent

(a) (b)

100 100
90 90
80 80
70 70
Yield ITM, %
Yield SQA, %

60 60
50 50
40 15 bar 40
30 30 bar 30
20 20
10 10 15 bar
30 bar
0 0
00:00 01:00 02:00 03:00 04:00 05:00
06:00 00:00 01:00 02:00 03:00 04:00 05:00
06:00
Time, hh:mm Time, hh:mm

Fig. 11. SQE hydrogenation: (a) pressure effect on SQA yield; (b) intermediates (ITM) yield. 2% Pd/ceramic
3 × 3 mm pellets, 180°C, 10% SQE (marine) in an organic solvent

intermediates and their isomers. Using gas were investigated. For this series of experiments,
chromatography-mass spectrometry (GC-MS), 99% SQE (marine source) was used to rule out the
more than 60 individual peaks of partially effect of vegetable SQE impurities.
hydrogenated intermediates and isomers have Comparison of different catalysts, using high
been identified, which were divided into six groups purity SQE (99%, Aldrich) showed that the best
based on their molecular weight (MW). Besides performance was obtained with 1 × 3 mm pellets
the SQE (MW 410) and SQA (MW 422) there were followed by 3 × 3 mm pellets and 3D printed crushed
six groups of partially hydrogenated intermediates catalyst that had slightly lower performance, see
differentiated by one double bond (H2) giving Figure 9. This result indicates that most probably
molecular masses MW 410, MW 412, MW 414, internal diffusion limitations take place and the
MW 416, MW 418 and MW 420. Among the effect is less important for 1 × 3 mm pellets.
undesired intermediates, cyclosqualane (MW 420) The impact of different operating conditions is
can be found. This presented a more significant discussed below. Figure 10 shows the temperature
peak in the GC-MS spectrum. Catalytic performance effect on relative SQE concentration and SQA yield
of different catalyst shapes as well as effect of profiles versus time. After about 3 h of reaction,
operating conditions on the hydrogenation process all SQE was practically converted at all reaction

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 https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)
temperatures, while the SQA yield reached only
54.5% at 160°C or 70% at 180°C respectively.
This observation most probably indicates that
the apparent activation energy of the subsequent
hydrogenation steps of individual C=C double
bonds increases with the degree of saturation.
Note that undesired side products of reaction such
as cyclosqualanes were not observed under these
conditions.
The effect of pressure is presented in Figure 11,
demonstrating that the formation of partially
saturated intermediates was favoured against SQE
at hydrogen pressure about 15 bar. Besides, high
pressure was necessary to reach high SQE yields.
The parametric study in a batch reactor provided
the necessary input about the optimal operating
conditions to conduct the SQE hydrogenation in a
continuous reactor.
Catalyst Deactivation in Batch
Reactor
In a batch reactor, a powder version of the catalysts
prepared was tested for stability. For this series
of experiments, vegetable SQE was used, with a
purity of 82% as it is expected that this would
be more representative of the behaviour of the
catalyst in the pilot plant. The reaction was carried
out for 4 h at 200°C and 20 bar of hydrogen.
The experimental results are shown in Figure 12.
The partially hydrogenated SQE intermediates are
presented as groups according to their GC-MS MW
starting from SQE and its isomers with MW 410
40
L1-fresh cat
L2-used 1x
35
L3-used 2x
L4-used 3x
30 L4a-used 4x
SQE left yields, %
25
20
15
10
5 94 0.03057 ºC mg
0 92.28%
SQE left 410 412 414 416 418 420 SQA
Mixture component
Fig. 12. Product composition after repeated use of
the catalyst, reaction time 4 h at 200°C and 20 bar,
Pd/ceramic
198 © 2019 Johnson Matthey
to SQA (MW 422). L1 represents the analyses
of the reaction products using a fresh catalyst.
Subsequently, L2 to L4 represent runs 2 to 4 using
the same catalyst and conditions with a fresh feed.
L4a, however, corresponds to the product of the
reaction after thoroughly washing the catalyst with
xylene. Both activity and selectivity decreased
after each cycle. A significant regeneration of both
SQE conversion and selectivity towards production
of SQA was observed in L4a.
This experiment followed a thorough washing of
the catalyst attempting its regeneration. A likely
explanation for recovering the activity and selectivity
is that the washing had removed intermediates of
the reaction deposited on the surface of the catalyst.
Some waxes were observed in the final product,
which tended to dissolve in the feed when hot.
Thermogravimetric experiments showed the
presence of a product in the used catalyst after
one use that decomposed at ca. 250°C, as shown
in Figure 13.
In a continuous reactor, the temperature should
be kept above 85°C to avoid solidification of the
waxes that occur on the surface of the catalyst.
In conventional methods for production of SQE
using Ni as the reducing agent, the metal tends
to leach onto the final product. In order to avoid
toxic metal in the SQA, a costly cleaning step is
required after reduction. Although the process
presented in this paper is Ni free, it was necessary
to determine whether Pd leaches into the final
product. Various Pd compounds have been proven
to induce sensitisation in several animal species
(11). It was thus necessary to test the levels of Pd
present in the final SQA. The Pd content for L1 and
L4a were analysed by inductively coupled plasma
Y-1 Y-3 Y-2
100 250.02 ºC 0.8
Temperature difference, ºC mg–1
93.93%
0.6366 ºC mg–1
0.6
98 600
Temperature, ºC
Weight, %
0.4
96 400
183.01 ºC 0.2
98.31% 303.97 ºC
–1 93.10%
–0.004993 ºC mg–1 200
0.0
–0.2
92
0 200 400 600 800
Temperature, ºC
Fig. 13. Thermogravimetric study of Pd/ceramic
catalyst after one use
https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

Table IV Comparison of SQE Hydrogenation Performed in Continuous Reactors of Different

Scales
Trickle-bed Pilot-plant Pilot-plant
Unit
milli-reactor reactor reactor
Catalyst – Conventional Conventional 3D printed
Reactor volume ml 10 324 324
Reactor diameter mm 8.5 22 22
Catalyst size mm Pellets 1 × 3 mm Pellets 3 × 3 mm 3D printed
SQE flowrate
g h–1 5.5 185 185
(20% in solvent)
Temperature °C 180 180 180
Pressure bar 25 25 25
Space velocity mmolPd h g–1SQE 20 20 20
SQE conversion % 99.5 100 100
SQA selectivity % 69.8 89 95.7

(a) (b)
30

25
Particle count

20

15

10

5
20 nm 0
1.60 2.40 3.20 4.00 4.80 5.60 more
Particle size, nm
Fig. 14. (a) TEM image for fresh catalyst; (b) particle size analysis for fresh catalyst

mass spectrometry (ICP-MS) to show levels of the
metal below 5 ppb. This proved the safety of using
this Pd catalyst for a cosmetic application. Both the
absence of Pd in the final product and the possibility
of regenerating the catalyst, suggested that the
catalyst was stable under the reaction conditions.
Continuous Hydrogenation
of Squalene in a Trickle-Bed
Milli-Reactor and a Pilot-Plant
A feasibility study was carried out to determine
whether it would be possible to perform the
hydrogenation of SQE in a continuous reactor.
A trickle-bed milli-reactor of a bed volume about
10 ml was employed to perform hydrogenation tests
with catalyst of conventional shape. The unit was
operated for several days while each experiment at
constant operating conditions took at least 6 h. At
180°C and 25 bar a stable SQE conversion 99.5%
with SQE yield 69.8% was obtained (see Table IV).
Catalyst deactivation was not observed in
the trickle-bed milli-reactor. However, the
transmission electron microscopy (TEM) images
of the spent catalyst showed a slight aggregation
of Pd particles after ca. 40 h of reaction, as
illustrated in Figures 14 and 15. Once the
hydrogenation process in continuous mode was
proven to be feasible in the trickle-bed milli-
reactor, experiments in a pilot-plant of volume
324 ml were approached under the same operating
conditions.
Continuous Pilot-Plant Squalene
Hydrogenation
The pilot-plant for continuous hydrogenation of
SQE is an automated, computer-controlled system
(which was developed and built by Advanced
Machinery & Technology Chemnitz GmbH within
the project PRINTCR3DIT).

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(a)
Particle count
20 nm
Fig. 15. (a) TEM image for catalyst after ca. 40 h in trickle-bed milli-reactor; (b) particle size analysis for
catalyst after ca. 40 h in trickle-bed milli-reactor
Fig. 16. Schematic of the continuous pilot-plant for
SQE hydrogenation
With the aim of transferring the SQE hydrogenation
from conventional batch to a continuous method
a tubular reactor was the most suitable choice. It
can be run as a trickle-bed reactor. The reactor
itself is made of stainless steel. Solid catalyst can
be loaded from the top of the reactor. Figure 16
represents a schematic of the pilot plant, with the
reactor highlighted by the red line.
State-of-the-art Catalyst
For the purpose of a benchmark, a state-of-the-art
catalyst supported on conventional 3  mm pellets
form (see Table II) was loaded into the reactor.
The catalyst was obtained following a proprietary
synthetic method from Johnson Matthey. This was
compared with a catalyst prepared using a 3D
printed ceramic support. No significant pressure
200 © 2019 Johnson Matthey
(b)
60
50
40
30
20
10
0
less 3.00 6.00 9.00 12.00 15.00 more
Particle size, nm
drop was observed between the top and the bottom
of the reactor.
This conventional catalyst allowed an excellent
conversion of SQE into SQA at temperatures from
180°C to 240°C with a pressure of 25–30 bar.
However, adjusting the temperature to 240°C and
the pressure to 30 bar resulted in high conversion
with an acceptable level of isomerisation.
3D Printed Catalyst
The 3D printed catalyst as a foam (see Table II)
was loaded into the reactor. The total weight of
the sample was 200 g, forming a catalyst bed of
75 cm high. As for the conventional catalyst, no
significant pressure drop was observed during this
trial between the top and the bottom of the bed.
Conversion and selectivity were high at low
temperatures with the 3D printed catalyst, which
differed from the low selectivity observed when
using conventional supports. The novel 3D printed
catalyst showed high selectivity towards SQA at
a temperature of 180°C and a pressure of 25 bar
(see Table IV). A possible explanation for this
improvement could be the fact that the geometry
of the foam enhanced the diffusion of SQE and
hydrogen on the surface of the metal.
The effect of temperature on the selectivity to
SQA was also investigated, as shown in Figure 17.
Operation at temperatures below 180°C allowed
good conversion of SQE. However, the selectivity
towards SQA becomes insufficient. Nevertheless,
at 240°C excellent conversion and selectivity were
obtained even for the 100 wt% vegetable SQE
feed.
The single load of 3D printed catalyst has produced
more than 15 kg of good quality SQA up to the time
of writing this article with no signs of deactivation.
https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)
100
90
80
70
60
50
%
40
30
20
10
0
140 160 180 200 220 240
Temperature, ºC
Fig. 17. Conversion of SQE and selectivity towards SQA at different temperatures, at liquid feed rate
250 g h–1, 75 wt% SQE in organic solvent, 25 bar, 3D printed catalyst
This suggests that the catalytically active phase
does not change during the process and the metal
does not significantly leach into the product. The
use of 3D printed technology allowed optimisation
of the reaction conditions and production of large
amounts of SQA using a more compact reactor
than current technologies.
Conclusions
In principle, it would be possible to carry out the
hydrogenation of SQE in a batch reactor with the
novel catalyst developed by Johnson Matthey.
However, it would require catalyst reactivation
between cycles. The use of a continuous reactor
presents the advantages of reusability of the
catalyst with no significant losses of activity or
selectivity. On the other hand, for a typical SQA
production plant, a batch reactor of ca. 1.5 m3
would be required, while a continuous system
could carry on the process with a volume of about
0.05 m3, 30 times smaller. Being able to control the
reaction rate along the reactor bed and preventing
formation of undesired isomers is a potential
advantage of the use of 3D printing technology.
The use of CFD modelling for the efficient design
of the support proved crucial in the success of
the experiments. Being able to directly print the
final catalytic support offered the advantage of
an alternative way to change the process, which
in turn, would allow higher levels of flexibility.
In addition, because of the use of a Pd catalyst,
the final product was Ni free, which removed the
cleaning step that would normally occur in the
manufacturing of SQA for the pharmaceutical and
cosmetic industries.
201 © 2019 Johnson Matthey
SQA, %
Conversion SQE,%
Acknowledgements
The authors acknowledge the financial support
given to the PRINTCR3DIT project by the European
Union’s Horizon 2020 research and innovation
programme under grant agreement No 680414.
The project belongs to the Sustainable Process
Industry through Resource and Energy Efficiency
(SPIRE) programme and information can be
found online. The authors would also like to thank
Daniel  G. Direito for preparing the STL files in
Blender® and Martha Briceno de Gutiérrez and
Trung Tran for the STEM images. Thanks to Gareth
Hatton for the EMPA study. Finally, the author
would like to acknowledge Paul Fisher and Raquel
García for their study on Pd leaching.
This contribution has been prepared using results
achieved within the open access infrastructure
belonging to the project Efficient Use of Energy
Resources Using Catalytic Processes (project code
LM2015039) which was financially supported by
the Ministry of Education, Youth and Sports of the
Czech Republic within the targeted support of large
infrastructures. The project has been integrated
into the National Sustainability Programme I of
the Ministry of Education, Youth and Sports of the
Czech Republic through the project Development
of the UniCRE Centre, project code LO1606.
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The Authors
Sonia Garcia obtained a BSc in Chemistry from the University of La Rioja, Spain. She joined
Johnson Matthey in 2001 where she worked on a Marie Curie funded PhD in Chemistry
from the University of Reading, UK, on nanocatalysts for fuel cell applications. Currently
she is working in the New Applications Group in Johnson Matthey on a variety of projects.

Stephen Poulston has a PhD in chemistry from the University of Cambridge, UK, and is
a research scientist at Johnson Matthey, Sonning Common, UK where he has worked
since 1998. Stephen has experience of a wide range of heterogeneous catalyst systems
including hydrogenation and platinum group metal catalysis.

Deena Modeshia obtained a MChem in 2006, followed by a PhD on hydrothermal synthesis

of mixed metal oxides, from the University of Warwick, UK, in 2010. She joined Johnson
Matthey in 2012 and has worked on several gas purification projects and currently works on
catalysts for improving the process of converting waste into useful products or hydrogen.

Petr Stavarek graduated in Chemical Engineering at VŠB - Technical University of Ostrava,

Czech Republic and pursued his PhD studies at the Institute of Chemical Technology,
Prague, Czech Republic. As a member of the Department of Multiphase Reactors at the
Institute of Chemical Process Fundamentals of the CAS, Prague, Czech Republic, he is
leader of a laboratory of microreactors. His main research interests are in microreaction
technology, microreactor design and process intensification for multiphase and catalytic
reactions.

202 © 2019 Johnson Matthey

https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

Massimo Ujčić graduated in Chemical Engineering at the Faculty of Chemical Engineering

and Technology, University of Zagreb, Croatia. In 2016 he joined the Department of
Multiphase Reactors at the Institute of Chemical Process Fundamentals of the CAS, Prague,
Czech Republic where he pursues PhD study. His research interests are in microreactor
design, 3D printing and process intensification for multiphase and catalytic reactions.

Farzad Lali graduated in 2008 in Chemical Engineering from RWTH Aachen University,
Aachen, Germany and obtained his PhD degree in 2015 from Dresden University of
Technology, Germany. His research interests are multiphase reactions, structured catalysts
and modelling and simulation. He was a postdoctoral fellow at the Department of Multiphase
Reactors of the Institute of Chemical Process Fundamentals of the CAS, Prague, Czech
Republic. He is currently working as a research associate at the Institute of Chemical
Engineering of the University of Ulm, Germany.

Manuel A. Alves graduated in 1995 in Chemical Engineering from the Faculty of Engineering
of the University of Porto (FEUP) and obtained a PhD degree in 2004 at the same institution.
He is an Associate Professor at FEUP and his main research interests are in complex fluids,
microfluidics and computational rheology.

José Daniel Araújo graduated in Chemical Engineering from the FEUP and obtained his PhD
degree at the same institution. The PhD work involved the design, operation and modelling
of a pilot scale setup based on a continuous structured packing bubble column reactor for
vanillin production from lignin oxidation. He joined the Transport Phenomena Research
Center (CEFT) at FEUP in 2008 and worked in several projects involving modelling and CFD
applied to multiphase flow, transport phenomena and process intensification.

Michael Krusche obtained his degree in physics from the Dresden University of Technology,
Germany, in 1980. He is Managing Director of Advanced Machinery & Technology Chemnitz
GmbH (AMTECH), Chemnitz, Germany, which he founded in 2010 emerging from his former
company AMTEC GmbH, Germany. The core competence of AMTECH is the development
and production of highly automated reactor systems, with applications especially in the
field of catalysis.

Frank Ullrich graduated in Chemistry at the Freiberg University of Mining and Technology,
Germany, in 2003 and obtained his PhD from the same university in 2008. At the same
time, he was a staff member of AMTEC GmbH. Currently, he is chief technology officer of
the company and primarily responsible for the development of AMTECH systems.

203 © 2019 Johnson Matthey

https://doi.org/10.1595/205651319X15535963555844 Johnson Matthey Technol. Rev., 2019, 63, (3)

Diana Maier graduated in Chemical Engineering at the Dresden University of Applied

Sciences, Germany, in 2006. She joined the Leibniz Institute for Solid State and Materials
Research (IFW) Dresden, Germany, where she conducted her PhD, followed by a PhD
degree from the Dresden University of Technology in 2011. Since 2012 she has been a
staff member of AMTECH.

204 © 2019 Johnson Matthey